Magnetic material and production method therefor

ABSTRACT

A production method for a magnetic material, which is expressed by a chemical structure formula Fe(Al 1−x Mn x ) 2 O 4 , where 0&lt;x&lt;1, and exhibits ferromagnetism, includes: preparing a mixed aqueous solution by dissolving, in distilled water, Fe nitrate, Al nitrate, and an oxide including Mn, the Fe nitrate, the Al nitrate, and the oxide being parent materials; preparing a metal-citric acid complex by mixing citric acid and ethylene glycol with the mixed aqueous solution; obtaining a precursor by boiling the metal-citric acid complex to a gel and drying the gel; and obtaining the magnetic material by sintering the precursor.

The present disclosure relates to a ferrite magnetic material which is ferromagnetic, and a production method therefor.

BACKGROUND ART

Conventionally, development of a magnetic material having high magnetic permeability μ in a high-frequency region has been expected. In recent years, a ferrite has attracted attention as such a material.

A ferrite is a ceramic mainly composed of iron oxide, and examples of the ferrite include Mg(Fe¹⁻Mn_(x))₂O₄, FeAl₂O₄ (hercynite), and the like. Moreover, ferrites are divided into a magnetic substance exhibiting magnetism and a non-magnetic substance exhibiting no magnetism. The magnetic substance, especially a ferromagnetic ferrite, is applied in various fields such as inductors for high frequency, magnetic cores for transformers, and black pigment powder for application. (See Patent Literature (PTL) 1, for example.)

PTL 1 discloses a ceramic burner as a technique using a ferrite.

CITATION LIST Patent Literature

-   [PTL 1] Japanese Unexamined Patent Application Publication No.     S62-112907

SUMMARY OF INVENTION Technical Problem

PTL 1 discloses, as a material of the ceramic burner, a ferrite having a spinel structure of MgAl₂O₄, FeAl₂O₄, CoAl₂O₄, or the like. The use of hercynite FeAl₂O₄, which is composed of Fe and Al, is sometimes especially desired depending on fields in which the ferrite is used.

However, hercynite FeAl₂O₄ is a non-magnetic substance, and thus cannot be used when it is desired to use the magnetic properties of the ferrite. In response, it has been desired to develop a magnetic material which is composed of Fe and Al and has high magnetic properties.

In view of the above problem, the present invention has an object to provide a magnetic material having high magnetic properties, and a production method therefor.

Solution to Problem

A magnetic material according to one aspect of the present disclosure is a magnetic material expressed by a chemical structure formula Fe(Al_(1−x)Mn_(x))₂O₄, where 0<x<1, and exhibits ferromagnetism.

Advantageous Effects of Invention

According to the present disclosure, it is possible to provide a magnetic material having high magnetic properties, and a production method therefor.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a flow chart illustrating a production process of Fe(Al_(1−x)Mn_(x))₂O₄ according to an embodiment.

FIG. 2 is a graph illustrating an X-ray diffraction pattern of Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0.

FIG. 3 is a graph illustrating an X-ray diffraction pattern of a product treated with heat under each of various gas atmospheres in the case x=0.2.

FIG. 4 is a graph illustrating an X-ray diffraction pattern of a product treated with heat under each of various gas atmospheres in the case x=0.4.

FIG. 5 is a graph illustrating an X-ray diffraction pattern of a product treated with heat under each of various gas atmospheres in the case x=0.5.

FIG. 6 is a graph illustrating an X-ray diffraction pattern of a product treated with heat under each of various gas atmospheres in the case x=0.6.

FIG. 7 is a graph illustrating an X-ray diffraction pattern of a product treated with heat under each of various gas atmospheres in the case x=0.8.

FIG. 8 is a graph illustrating an X-ray diffraction pattern of a product obtained under each of gas atmospheres generated by Fe(Al_(1−x)Mn_(x))₂O₄ indicating a spinel structure.

FIG. 9A is a table summarizing products when a value of x and a content rate of H₂ are changed.

FIG. 9B is a graph illustrating an X-ray diffraction pattern of a product produced by pulsed electric-current pressure sintering in the case x=0.5.

FIG. 9C is a graph illustrating X-ray diffraction patterns of products produced by pulsed electric-current pressure sintering and atmospheric heat treatment in the case x=0.5.

FIG. 10A is a scanning electron microscopy (SEM) photograph of Fe(Al_(1−x)Mn_(x))₂O₄ powder in the case x=0.

FIG. 10B is an SEM photograph of Fe(Al_(1−x)Mn_(x))₂O₄ powder in the case x=0.2.

FIG. 10C is an SEM photograph of Fe(Al¹⁻Mn_(x))₂O₄ powder in the case x=0.4.

FIG. 10D is an SEM photograph of Fe(Al_(1−x)Mn_(x))₂O₄ powder in the case x=0.5.

FIG. 10E is an SEM photograph of Fe(Al¹⁻Mn_(x))₂O₄ powder in the case x=0.6.

FIG. 10F is an SEM photograph of Fe(Al_(1−x)Mn_(x))₂O₄ powder in the case x=0.8.

FIG. 10G is an SEM photograph of Fe(Al_(1−x)Mn_(x))₂O₄ powder in the case x=1.0.

FIG. 11 is a graph illustrating a relationship between a value of x and a lattice parameter of Fe(Al_(1−x)Mn_(x))₂O₄.

FIG. 12A is a graph illustrating B—H characteristics of Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0.

FIG. 12B is a graph illustrating B—H characteristics of Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0.2.

FIG. 12C is a graph illustrating B—H characteristics of Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0.6.

FIG. 12D is a graph illustrating B—H characteristics of Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0.7.

FIG. 12E is a graph illustrating B—H characteristics of Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0.8.

FIG. 12F is a graph illustrating B—H characteristics of Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0.9.

FIG. 13 is a graph illustrating a relationship between a value of x in Fe(Al_(1−x)Mn_(x))₂O₄ and mass magnetic susceptibility σ_(s).

FIG. 14 is a graph illustrating a relationship between a value of x in Fe(Al_(1−x)Mn_(x))₂O₄ and a saturation magnetic flux density B_(s).

FIG. 15 is a graph illustrating a relationship between a value of x in Fe(Al_(1−x)Mn_(x))₂O₄ and log H_(c).

FIG. 16 is a table summarizing a relationship between values of x in Fe(Al_(1−x)Mn_(x))₂O₄ and magnetic properties.

DESCRIPTION OF EMBODIMENTS (Underlying Knowledge Forming Basis of the Present Disclosure)

The underlying knowledge forming the basis of the present disclosure will be described prior to describing embodiments of a magnetic material and a production method therefor according to the present disclosure.

As stated above, hercynite FeAl₂O₄, a type of ferrite, is a non-magnetic substance and exhibits no ferromagnetism. In order to produce a magnetic material exhibiting high magnetic properties, the inventors of the present application have tried to develop a ferrite magnetic material which exhibits ferromagnetism and has a new composition, by adding Mn, as the fourth element other than Fe, Al, and O, to hercynite FeAl₂O₄. The inventors, however, have found out that it is difficult to prepare a powder using the conventional solid reaction method, sol-gel method, and citric acid gel method, and it is not possible to synthesize such a complex magnetic material. The inventors have gained the following knowledge from these experimental results.

When the structure of ferrite is expressed as AB₂O₄ (where A and B are elements), ferrite having a new composition is expressed as Fe(Al_(1−x)Mn_(x))₂O₄. In hercynite FeAl₂O₄, Fe in A site is divalent and Al in B site is trivalent. Accordingly, in ferrite having the new composition, Fe in A site must be divalent and Mn in B site must be trivalent.

Here, to produce hercynite FeAl₂O₄ using the solid reaction method, it is assumed that after α-Fe₂O₃(Fe³⁺) and fine γ-Al₂O₃ as parent materials are evenly mixed, α-Fe₂O₃(Fe³⁺) and γ-Al₂O₃ are heat-treated at 900° C. in N₂ gas containing a little less than 1% of H₂, Fe³⁺ is reduced to Fe²⁺, and FeAl₂O₄ is synthesized. If, however, the solid reaction method is applied to ferrite Fe(Al_(1−x)Mn_(x))₂O₄ having a new composition, Mn in Mn oxide, a raw material, is reduced to Mn²⁺ and is thus placed in A site. Accordingly, it is difficult to obtain Fe(Al_(1−x)Mn_(x))₂O₄ in which part of Al in B site of Fe(Al_(1−x)Mn_(x))₂O₄ is replaced with Mn.

Moreover, with the sol-gel method which uses the hydrolysis of metal alkoxide, and the citric acid gel method which forms a metal complex by adding citric acid and ethylene glycol to a mixed aqueous solution of metal nitrate, then removes organic components by heating the metal complex in the atmosphere, and finally synthesizes a powder by further heating the metal complex at high temperature, it is difficult to control a heat treatment atmosphere which allows Fe²⁺ and Mn³⁺ to be simultaneously present, and to obtain targeted ferrite Fe(Al_(1−x)Mn_(x))₂O₄ having a new composition.

In view of this, a magnetic material according to one aspect of the present disclosure is a magnetic material expressed by a chemical structure formula Fe(Al_(1−x)Mn_(x))₂O₄, where 0<x<1, and exhibits ferromagnetism.

With this configuration, it is possible to provide a magnetic material having high magnetic properties.

Moreover, a range of a value of mass magnetic susceptibility σ_(s) [emu/g] of the magnetic material may be expressed as σ_(s)≧10.

With this configuration, it is possible to obtain a magnetic material suitable as a material of a device which is required to have high magnetic properties.

Moreover, a range of a value of x may be expressed as x≧0.2.

With this configuration, it is possible to obtain a magnetic material suitable as a material of a device which is required to have high magnetic properties.

Moreover, the magnetic material comprises manganese dioxide MnO₂ as a raw material.

With this configuration, it is possible to place Mn in the same site as a site in which Al of hercynite FeAl₂O₄ is placed, it is possible to easily synthesize a ferrite magnetic material expressed by the chemical structure formula Fe(Al_(1−x)Mn_(x))₂O₄.

Moreover, a production method for a magnetic material according to one aspect of the present disclosure is a production method for a magnetic material, which is expressed by a chemical structure formula Fe(Al_(1−x)Mn_(x))₂O₄, where 0<x<1, and exhibits ferromagnetism, the production method including: preparing a mixed aqueous solution by dissolving, in distilled water, Fe nitrate, Al nitrate, and an oxide including Mn, the Fe nitrate, the Al nitrate, and the oxide being parent materials; preparing a metal-citric acid complex by mixing citric acid and ethylene glycol with the mixed aqueous solution; obtaining a precursor by boiling the metal-citric acid complex to a gel and drying the gel; and obtaining the magnetic material by sintering the precursor.

With this configuration, it is possible to provide a magnetic material having high magnetic properties.

Moreover, in the obtaining of the magnetic material, a trivalent Fe ion and a tetravalent Mn ion may be reduced to a divalent Fe ion and a trivalent Mn ion, respectively.

With this configuration, it is possible to place Mn in the same site as a site in which Al of hercynite FeAl₂O₄ is placed, it is possible to easily synthesize a ferrite magnetic material expressed by the chemical structure formula Fe(Al_(1−x)Mn_(x))₂O₄.

Moreover, the Fe nitrate may be iron(III) nitrate nonahydrate Fe(NO₃)₃.9H₂O, the Al nitrate may be aluminum(III) nitrate nonahydrate Al(NO₃)₂.9H₂O, and the oxide including Mn may be manganese dioxide MnO₂.

With this configuration, it is possible to place Mn in the same site as a site in which Al of hercynite FeAl₂O₄ is placed, it is possible to easily synthesize a ferrite magnetic material expressed by the chemical structure formula Fe(Al_(1−x)Mn_(x))₂O₄.

Moreover, in the preparing of the metal-citric acid complex, a molar ratio among a metal ion, the citric acid, and the ethylene glycol in the mixed aqueous solution may be 1:3:9.

With this configuration, it is possible to easily synthesize a ferrite magnetic material expressed by a chemical structure formula Fe(Al_(1−x)Mn_(x))₂O₄ of a single phase.

Hereinafter, embodiments will be described in detail with reference to the drawings.

It is to be noted that the embodiments described below each show a specific example of the present disclosure. The numerical values, shapes, materials, structural elements, the arrangement and connection of the structural elements, steps, order of the steps, etc. indicated in the following embodiments are mere examples, and therefore are not intended to limit the present disclosure. Moreover, among the structural elements in the following embodiments, structural elements not recited in any of the independent claims indicating the broadest inventive concepts are described as optional elements.

Embodiment [1. Definitions of Terms]

First, the definitions of terms used in an embodiment will be provided.

A citric acid gel method (or polymerized complex method) is defined as the following material production method. First, a stable chelate complex (metal-citric acid complex) is produced using various types of metal ions and citric acid. Ethylene glycol is added to the metal-citric acid complex, and the metal-citric acid complex is dissolved and dispersed in ethylene glycol. Ethylene glycol in which the metal-citric acid complex is dispersed is esterified by heating and polymerization, and the metal-citric acid complex (polymer metal complex) is evenly trapped in polyester. In other words, ethylene glycol is added to the metal-citric acid complex and esterified by heating and polymerization to obtain a gel. Subsequently, the gelled metal-citric acid complex is calcined (prebaked and baked) to synthesize an oxide, that is, a targeted substance.

The network structure of the polymer metal complex obtained by the citric acid gel method (or polymerized complex method) is formed mainly by ester polymerization and copolymerization, and is chemically stable. Accordingly, the mobility of metal ions is low, and provided is an operation advantage of reducing aggregation or segregation of metal elements in a subsequent calcination stage.

A solid phase method is defined as the following material production method. Various types of raw material powders to be parent materials are weighed in at a predetermined amount, and mixed. After the mixing, the mixture is first temporarily baked and then baked. Accordingly, a targeted substance is synthesized. It is to be noted that the solid phase method is also referred to as a solid reaction method.

A lattice parameter is one of parameters used as crystal data, and a significant element for identifying a substance. Lattice parameters are represented by lengths a, b, c of the sides of a unit lattice in a crystal lattice and angles α, β, γ between the sides.

Moreover, application of a magnetic field to a magnetic substance causes a magnetic moment to orient to a magnetic field direction, which results in magnetization. In other words, magnetization is referred to causing a magnetic moment to point to one direction by applying a magnetic field to a magnetic substance. Moreover, the magnetizing properties of a magnetic substance are generally irreversible and change curvilinearly. Such irreversible characteristics of the magnetic substance are referred to as hysteresis.

Moreover, the magnetic moment of a magnetized substance is also referred to as magnetic susceptibility [emu]. In this case, the magnetic susceptibility is represented by a vector and indicates the intensity of magnetization. A magnetic moment per unit volume is referred to as bulk magnetic susceptibility [emu/cm³], and a magnetic moment per unit mass is referred to as mass magnetic susceptibility [emu/g]. These indicate the intensity of magnetization. It is to be noted that mass magnetic susceptibility σ_(s) may be simply referred to as “magnetic susceptibility” in the embodiment described below.

Moreover, the intensity of magnetization when a magnetic field is applied to a magnetic substance until the magnetic field is saturated is referred to as saturation magnetic susceptibility J.

Moreover, magnetic flux density B[T] refers to surface density of magnetic flux per unit area, and may be simply referred to as a magnetic field strength. In addition, magnetic flux density B corresponding to saturation magnetic susceptibility J_(s) is referred to as saturation magnetic flux density B_(s)[T]. It is to be noted that regarding saturation magnetic flux density B_(s), a point at which the intensity of magnetization reaches saturation is referred to as S point.

Removal of the magnetic field after saturation magnetization does not cause the intensity of the magnetization to be zero due to hysteresis, and magnetization having a certain intensity remains. The intensity of the magnetization is referred to as residual magnetization J_(r). Furthermore, application of a reverse magnetic field to a magnetic substance in a state of residual magnetization causes the intensity of magnetization in an applied magnetic field having a certain intensity to be zero. The intensity of the magnetic field at this time is referred to as coercivity H_(c) [Oe]. A substance having a small coercivity is referred to as a soft magnetic material. In contrast, a substance having a high coercivity is referred to as a hard magnetic material (e.g., a permanent magnet). The value of coercivity greatly changes depending on a magnetic material.

Magnetic permeability μ refers to an index indicating how easily a magnetic flux passes through a magnetic material, that is, the degree of a magnetic flux variation when a magnetic field having a certain intensity is applied. The magnetic permeability indicates ease of magnetization, and is one of factors for evaluating the characteristics of a magnetic substance.

Like the magnetic permeability, an index indicating a relationship between a magnetic field and magnetization is referred to as magnetic susceptibility (magnetizability). Generally, magnetic susceptibility X is defined with the following equation.

X=J/H

Here, H represents a magnetic field, and 3 represents the intensity of magnetization. As expressed by the above equation, when a magnetic field affects a magnetic substance, the magnetization is a function of the magnetic field.

Moreover, a material having high permeable characteristics by which a higher magnetic flux density is induced by applying a slight magnetic field from outside is referred to as a highly magnetic permeable material or soft magnetic material. A highly magnetic permeable material is required to have a high magnetic permeability μ, a low coercivity H_(c), and a high saturation magnetic flux density B_(s), and have a small loss. Ferrite as a soft magnetic material, an oxide, generally has a high electrical resistance, and can be usually used for high frequency.

[2. Composition of Ferrite Fe(Al_(1−x)Mn_(x))₂O₄]

A magnetic material according to the embodiment is ferrite Fe(Al_(1−x)Mn_(x))₂O₄, an oxide containing Fe, Al, and Mn.

The structure of ferrite can be generally represented as AB₂O₄ (where A and B are any metal elements.). Ferrite according to the embodiment has a structure in which Fe is in A site and Al and Mn are in B site, and a composition in which part of Al in B site of hercynite FeAl₂O₄, known as a type of ferrite, is replaced with Mn.

Ferrite Fe(Al_(1−x)Mn_(x))₂O₄ according to the embodiment not only has the same characteristics as hercynite containing Fe and Al as components, but also has ferromagnetism that hercynite lacks.

[3. Production Method for Ferrite Fe(Al_(1−x)Mn_(x))₂O₄]

Hereinafter, a production method for ferrite Fe(Al_(1−x)Mn_(x))₂O₄ according to the embodiment will be described.

The production method for ferrite Fe(Al_(1−x)Mn_(x))₂O₄ according to the embodiment is obtained by modifying the aforementioned citric acid gel method. In the citric acid gel method, the following are used: iron(III) nitrate nonahydrate Fe(NO₃)₃.9H₂O and aluminum(III) nitrate nonahydrate Al(NO₃)₃.9H₂O, metal nitrate, as sources of metal elements of ferrite Fe(Al_(1−x)Mn_(x))₂O₄; and manganese(II) nitrate hexahydrate Mn(NO₃)₂.6H₂O as a source of Mn.

In contrast, in the production method for ferrite Fe(Al_(1−x)Mn_(x))₂O₄ according to the embodiment, the following are used: iron(III) nitrate nonahydrate Fe(NO₃)₃.9H₂O and aluminum(III) nitrate nonahydrate Al(NO₃)₃.9H₂O, metal nitrate, as sources of metal elements of ferrite Fe(Al_(1−x)Mn_(x))₂O₄. In addition, manganese dioxide MnO₂(Mn⁴⁺) is used as a source of Mn. Specifically, a mixed aqueous solution is prepared by evenly mixing fine particles of manganese dioxide MnO₂ with a nitrate aqueous solution in which iron(III) nitrate nonahydrate Fe(NO₃)₃.9H₂O and aluminum(III) nitrate nonahydrate Al(NO₃)₃.9H₂O are mixed.

Moreover, citric acid and ethylene glycol are mixed with the mixed aqueous solution, and the mixed aqueous solution is treated with heat under each of various gas atmospheres after organic components are removed. With this, Fe(Al_(1−x)Mn_(x))₂O₄ is synthesized by reducing trivalent Fe ions Fe³⁺ and tetravalent Mn ions Mn⁴⁺ to divalent Fe ions Fe²⁺ and trivalent Mn ions Mn³⁺, respectively. It is to be noted that hereinafter, ferrite Fe(Al_(1−x)Mn_(x))₂O₄, a new material, is simply shown as Fe(Al_(1−x)Mn_(x))₂O₄, iron(III) nitrate nonahydrate Fe(NO₃)₃.9H₂O is simply shown as Fe(NO₃)₃.9H₂O, aluminum(III) nitrate nonahydrate Al(NO₃)₃.9H₂O is simply shown as Al(NO₃)₃.9H₂O, and manganese dioxide MnO₂ is simply shown as MnO₂.

Hereinafter, the production method will be described in details.

FIG. 1 is a flow chart illustrating a production process of a ferrite magnetic material according to the embodiment.

As illustrated in FIG. 1, first, a solution 1 a, a solution 1 b, and a solution 1 c are prepared.

The solution 1 a contains, as parent materials, Fe(NO₃)₃.9H₂O and Al(NO₃)₃.9H₂O, metal nitrate, and MnO₂ as a source of Mn. Both Fe(NO₃)₃.9H₂O and Al(NO₃)₃.9H₂O contain H₂O, and are thus soluble and mixable. In addition, Fe in Fe(NO₃)₃.9H₂O and Al in Al(NO₃)₃.9H₂O become ions in an aqueous solution, and are present as Fe³⁺ and Al³⁺. Fe and Al are evenly dispersed in the aqueous solution by being ionized. It is to be noted that it is desirable that to make MnO₂ dispersible in an aqueous solution, particulate powder MnO₂ having a diameter of at most 0.5 μm be used.

The solution 1 b is a citric acid C₃H₄(OH)(COOH)₃ solution. It is to be noted that citric acid used here may be anhydrous citric acid (C(CH₂COOH)₂(OH)(COOH)) or citric acid monohydrate C₆H₈O₇.H₂O.

The solution 1 c is an ethylene glycol HOCH₂CH₂OH solution.

Next, the solution 1 a, the solution 1 b, and the solution is are mixed (step S1). It is desirable that where a total number of moles of metal ions contained in the solution 1 a is 1, a mixture ratio between the solution 1 b and the solution is be 3 to 9.

Subsequently, a mixed solution obtained by mixing the solution 1 a, the solution 1 b, and the solution 1 c is boiled at 120° C. for 48 hours (step S10). At this time, the mixed solution containing the solution 1 a, the solution 1 b, and the solution 1 c is heated while being stirred. Consequently, the mixed solution containing the solution 1 a, the solution 1 b, and the solution 1 c is gelled.

Next, the gelled mixed solution is dried at 25° C. in an atmosphere for 12 hours. As a result, a precursor of Fe(Al_(1−x)Mn_(x))₂O₄ is formed (step S12).

Next, the dried precursor of Fe(Al_(1−x)Mn_(x))₂O₄ is treated with heat (step S14). The heat treatment is performed at 300° C. in an atmosphere for 12 hours. Consequently, organic components in the precursor are removed. It is to be noted that the precursor after the heat treatment is amorphous.

Subsequently, the precursor of Fe(Al_(1−x)Mn_(x))₂O₄ is prebaked and crystallized. Examples of the prebaking include atmospheric heat treatment.

Specifically, first, the heat-treated precursor of Fe(Al_(1−x)Mn_(x))₂O₄ is put into a mold and compressed. At this time, uniaxial pressing is performed with a constant pressure of 98 Mpa (step S16).

Next, the compressed precursor of Fe(Al_(1−x)Mn_(x))₂O₄ is prebaked at 900° C. for two hours. At this time, the compressed precursor of Fe(Al_(1−x)Mn_(x))₂O₄ is calcined while N₂ gas containing H₂ gas at a predetermined rate is being released (step S18). The rate a % of H₂ gas is, for example, a=0, 0.01, 0.03, 0.05, 0.08, 0.1. In consequence, the amorphous precursor of Fe(Al_(1−x)Mn_(x))₂O₄ is crystallized. At this time, trivalent Fe ions Fe³⁺ is reduced to divalent Fe ions Fe²⁺, and tetravalent Mn ions Mn⁴⁺ is reduced to trivalent Mn ions Mn³⁺. Accordingly, the trivalent Mn ions Mn³⁺ are allowed to be placed in B site in the structure of ferrite expressed by a generic chemical structure formula AB₂O₄ (where A and B are any metal elements). As a result, trivalent ions Al³⁺ and Mn³⁺ are placed in B site. Ferrite Fe(Al_(1−x)Mn_(x))₂O₄ powder having the composition in which part of Al in hercynite FeAl₂O₄ is replaced with Mn is obtained through the above steps.

Subsequently, the ferrite Fe(Al_(1−x)Mn_(x))₂O₄ powder is sintered (step S20). It is to be noted that examples of sintering include atmospheric heat treatment to be performed after a prebaked precursor is formed by uniaxial pressing again, hot pressing, and the like. Here, the hot pressing refers to a method for placing a powder or a preformed material in a mold and pressure sintering the powder or the preformed material while heating the powder or the preformed material at high temperature. The hot pressing makes it possible to not only provide a closely-packed sintered body having a density close to a theoretical density, but also control the microstructure of a sintered body. Accordingly, the hot pressing makes it possible to form a sintered body having superior mechanical and physical properties, such as a high-strength sintered body. In addition, the hot pressing is characterized by improving an interfacial contact between different materials, binding crystals or different materials, and the like. The present disclosure is not limited to these methods, and another method for sintering Fe(Al_(1−x)Mn_(x))₂O₄ powder may be used. Moreover, the temperatures and times in the aforementioned steps are mere examples, and other temperatures and times may be used.

Various kinds of Fe(Al_(1−x)Mn_(x))₂O₄ powders were produced using the aforementioned production method while the value of x in Fe(Al¹⁻Mn_(x))₂O₄ was being changed. The value of x was set to be one of seven values as x=0, 0.2, 0.4, 0.5, 0.6, 0.7, 0.8. Moreover, the following evaluation was performed regarding the crystal structure and magnetic properties of each Fe(Al_(1−x)Mn_(x))₂O₄ powder resulting from prebaking and synthesizing.

[4. Evaluation of Crystal Structure of Ferrite Fe(Al_(1−x)Mn_(x))₂O₄]

As stated above, an evaluation was performed regarding the crystal structure of each Fe(Al_(1−x)Mn_(x))₂O₄ in the case where the value of x was changed as x=0, 0.2, 0.4, 0.5, 0.6, 0.7, 0.8.

FIG. 2 to FIG. 7 each are a graph illustrating an X-ray diffraction pattern of a product obtained by heat-treating a powder corresponding to a composition x=0, 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, under each of various gas atmospheres. FIG. 8 is a graph illustrating gas atmospheres and X-ray diffraction patterns of Fe(Al_(1−x)Mn_(x))₂O₄ whose crystal structure has become a spinel-type crystal structure after heat treatment, in the case x=0, 0.2, 0.4, 0.5, 0.6, 0.7, 0.8.

Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0 corresponds to FeAl₂O₄ (hercynite). As illustrated in FIG. 2, the X-ray diffraction pattern of Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0 matched the X-ray diffraction pattern of FeAl₂O₄ having a spinel-type crystal structure.

In the case x=0.2, Fe(Al_(1−x)Mn_(x))₂O₄ was produced while a rate a % of H₂ gas flowing into N₂ gas atmosphere was being changed as a =0, 0.01, 0.03, 0.05, 0.08 in the prebaking step. As illustrated in FIG. 3, in the case a=0, 0.01, 0.03, peak patterns were observed which matched the X-ray diffraction patterns of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄, Al₂O₃, and Fe₃O₄. Accordingly, it was confirmed that Al₂O₃ and Fe₃O₄ had been produced other than Fe(Al_(1−x)Mn_(x))₂O₄. Moreover, in the case a=0.05, 0.08, peak patterns were observed which matched the X-ray diffraction patterns of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄. Accordingly, it was confirmed that Fe(Al_(1−x)Mn_(x))₂O₄ powders of the spinel type had been synthesized.

In the case x=0.4, Fe(Al_(1−x)Mn_(x))₂O₄ was synthesized while a rate a % of H₂ gas included in N₂ gas was being changed as a=0, 0.01, 0.03, 0.05, 0.065, 0.08 in the prebaking step. As illustrated in FIG. 4, in the case a=0, 0.01, 0.03, 0.065, peak patterns were observed which matched the X-ray diffraction patterns of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄, Al₂O₃, and Fe₂O₃. Accordingly, it was confirmed that Al₂ 0 ₃ and Fe₂O₃ had been produced other than Fe(Al_(1−x)Mn_(x))₂O₄. Moreover, in the case a=0.05, peak patterns were observed which matched the X-ray diffraction patterns of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄, Fe₂O₃, and FeAl₂O₄. Accordingly, it was confirmed that Fe₂O₃ and FeAl₂O₄ had been produced other than Fe(Al_(1−x)Mn_(x))₂O₄. Moreover, in the case a=0.08, peak patterns were observed which matched the X-ray diffraction patterns of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄, Fe₂O₃, FeAl₂O₄, and MnO. Accordingly, it was confirmed that Fe₂O₃, FeAl₂O₄, and MnO had been produced other than Fe(Al_(1−x)Mn_(x))₂O₄.

In the case x=0.5, Fe(Al_(1−x)Mn_(x))₂O₄ was synthesized while a rate a % of H₂ gas included in N₂ gas was being changed as a=0.01, 0.03, 0.05, 0.08, 0.1 in the prebaking step. As illustrated in FIG. 5, in the case a=0.01, 0.03, 0.05, peak patterns were observed which matched the X-ray diffraction patterns of spinel-type Fe(Al¹⁻Mn_(x))₂O₄ and Al₂O₃. Accordingly, it was confirmed that Al₂O₃ had been produced other than Fe(Al_(1−x)Mn_(x))₂O₄. Moreover, in the case a=0.08, peak patterns were observed which matched the X-ray diffraction patterns of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄ and MnO. Accordingly, it was confirmed that Fe(Al¹⁻Mn_(x))₂O₄ and MnO had been produced. Moreover, in the case a=0.1, peak patterns were observed which matched the X-ray diffraction patterns of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄ (a theoretical value) and MnO. Accordingly, it was confirmed that Fe(Al_(1−x)Mn_(x))₂O₄ and MnO had been produced.

In the case x=0.6, Fe(Al_(1−x)Mn_(x))₂O₄ was produced while a rate a % of H₂ gas included in N₂ gas was being changed as a=0, 0.01, 0.03, 0.05, 0.08 in the sintering step. As illustrated in FIG. 6, in the case a=0, peak patterns were observed which matched the X-ray diffraction patterns of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄ and MnFe₂O₄. Accordingly, it was confirmed that MnFe₂O₄ had been formed other than Fe(Al_(1−x)Mn_(x))₂O₄. Moreover, in the case a=0.01, a peak pattern was observed which matched the X-ray diffraction pattern of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄. Accordingly, it was confirmed that Fe(Al_(1−x)Mn_(x))₂O₄ had been produced.

Moreover, in the case a=0.03, 0.05, 0.08, peak patterns were observed which matched the X-ray diffraction patterns of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄ and MnO. Accordingly, it was confirmed that Fe(Al_(1−x)Mn_(x))₂O₄ and MnO had been produced.

In the case x=0.8, Fe(Al_(1−x)Mn_(x))₂O₄ was produced while a rate a % of H₂ gas included in N₂ gas was being changed as a=0, 0.01, 0.03, 0.05, 0.08 in the prebaking step. As illustrated in FIG. 7, in the case a=0, 0.01, a peak pattern was observed which matched the X-ray diffraction pattern of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄. Accordingly, it was confirmed that Fe(Al_(1−x)Mn_(x))₂O₄ had been formed. Moreover, in the case a=0.03, 0.05, 0.08, peak patterns were observed which matched the X-ray diffraction patterns of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄ and MnO. Accordingly, it was confirmed that Fe(Al_(1−x)Mn_(x))₂O₄ and MnO had been produced.

In summarizing the case where only spinel-type Fe(Al_(1−x)Mn_(x))₂O₄ (single phase) was produced, as illustrated in FIG. 8, the value of x in Fe(Al_(1−x)Mn_(x))₂O₄ and the rate a % of H₂ gas included in N₂ gas in the prebaking were set to be (x, a)=(0.2, 0.08), (0.6, 0), (0.7, 0), (0.8, 0), (0.9, 0), the peak pattern was observed which matched the X-ray diffraction pattern of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄. Accordingly, it was confirmed that Fe(Al_(1−x)Mn_(x))₂O₄ had been produced. Moreover, in the case (x, a)=(0.2, 0.08), the peak patterns were observed which matched the X-ray diffraction patterns of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄ and FeAl₂O₄. Accordingly, it was confirmed that FeAl₂O₄ had been produced other than Fe(Al_(1−x)Mn_(x))₂O₄. Moreover, in the case (x, a)=(0.9, 0), the peak patterns were observed which matched the X-ray diffraction patterns of spinel-type Fe(Al_(1−x)Mn_(x))₂O₄ and MnFe₂O₄. Accordingly, it was confirmed that MnFe₂O₄ had been produced other than Fe(Al_(1−x)Mn_(x))₂O₄.

FIG. 9A is a table summarizing products when a value of x and a content rate of H₂ are changed. It is to be noted that in FIG. 9A, “S” indicates that a compound having a spinel-type crystal structure has been formed. In addition, a shaded cell for combination (x, a) indicates a combination (x, a) for which Fe(Al_(1−x)Mn_(x))₂O₄ of the spinel type has been confirmed.

In summary, as illustrated in FIG. 9A, it was found that the production of Fe(Al_(1−x)Mn_(x))₂O₄ of the spinel type had been confirmed in the case (x, a)=(0.2, 0.05), (0.2, 0.08), (0.6, 0), (0.6, 0.01), (0.7, 0), (0.7, 0.01), (0.8, 0), (0.8, 0.01), (0.9, 0), (0.9, 0.01).

It is to be noted that as illustrated in FIG. 9A, although it was not confirmed that Fe(Al_(1−x)Mn_(x))₂O₄ powder of the spinel type had been produced by merely heat-treating a precursor having a composition of x=0.5 under an atmosphere, it was confirmed that Fe(Al_(1−x)Mn_(x))₂O₄ of the spinel type had been produced even in the case x=0.5, in the following cases.

FIG. 9B is a graph illustrating an X-ray diffraction pattern of a product produced by pulsed electric-current pressure sintering (PECPS) in the case x=0.5. FIG. 9C is a graph illustrating X-ray diffraction patterns of products produced by pulsed electric-current pressure sintering and atmospheric heat treatment in the case x=0.5.

In the case x=0.5, a precursor of Fe(Al_(1−x)Mn_(x))₂O₄ was formed at a pressure of 50 MPa, and further the pulsed electric-current pressure sintering was performed on the precursor under the condition of 600° C./10 minutes/50 MPa/vacuum. An X-ray diffraction pattern of the product at this time was measured, and the X-ray diffraction pattern shown in FIG. 9B was obtained. In the X-ray diffraction pattern shown in FIG. 9B, a peak pattern was observed which matched a diffraction pattern of Fe(Al_(1−x)Mn_(x))₂O₄ of the spinel type. Accordingly, it was confirmed that Fe(Al_(1−x)Mn_(x))₂O₄ of the spinel type had been produced. It is to be noted that a sintering method is not limited to the pulsed electric-current pressure sintering, and may be another sintering.

Moreover, Fe(Al_(1−x)Mn_(x))₂O₄ powder of the spinel type produced by the pulsed electric-current pressure sintering was heat-treated at 900° C. for two hours under the atmosphere. An X-ray diffraction pattern of the product at this time was measured, and the X-ray diffraction pattern shown in FIG. 9C was obtained. It was found that although the X-ray diffraction pattern shown in FIG. 9C had become stronger in XRD than the X-ray diffraction pattern shown in FIG. 9B, part of a crystal phase had been separated. Accordingly, in the case x=0.5, to produce Fe(Al_(1−x)Mn_(x))₂O₄ powder of the spinel type, it can be said that performing only the PECPS is most suitable.

FIG. 10A to FIG. 10G are scanning electron microscopy (SEM) photographs of agglomerated particles of Fe(Al_(1−x)Mn_(x))₂O₄ powders in the case x=0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0. As illustrated in FIG. 10A to FIG. 10G, primary particles included in the agglomerated particles of Fe(Al_(1−x)Mn_(x))₂O₄ increase in particle diameter with increase in a value of x as in x=0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0.

FIG. 11 is a graph illustrating a relationship between a value of x and a lattice parameter of Fe(Al_(1−x)Mn_(x))₂O₄.

As illustrated in FIG. 11, the lattice parameter of Fe(Al_(1−x)Mn_(x))₂O₄ increases with increase in the value of x. It can be said that this is consistent with the result that the primary particles increase with increase in the value of x as in x=0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0 in FIG. 10A to FIG. 10G.

[5. Evaluation of Magnetic Properties of Ferrite Fe(Al_(1−x)Mn_(x))₂O₄]

Next, magnetic properties of Fe(Al_(1−x)Mn_(x))₂O₄ will be described.

FIG. 12A to FIG. 12F each are a graph illustrating B—H characteristics of Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0, 0.2, 0.6, 0.7, 0.8, 0.9. It is to be noted that although the scales of the vertical axis and horizontal axis are omitted for convenience in FIG. 12A to FIG. 12F, the magnitude of the scales is standardized in FIG. 12A to FIG. 12F.

The B—H characteristics show a change in magnetic flux density (B indicated by the vertical axis) when an external magnetic field (H indicated by the horizontal axis) is applied to a material. The B—H characteristics are represented by a line (proportion) for a paramagnetic substance, and are represented by what is called a hysteresis curve for a ferromagnetic substance. Moreover, a material having a small difference between positive and negative values (coercivity H_(c)) of the external magnetic field H when the magnetic flux density is 0 (a low coercivity H_(c)) in the hysteresis curve is referred to as a soft magnetic material, and a material having a large difference between positive and negative values of the external magnetic field H when the magnetic flux density is 0 (a high coercivity H_(c)) in the hysteresis curve is referred to as a hard magnetic material. A material is magnetized faster by the external magnetic field as the material has a smaller difference between positive and negative values of H (lower coercivity H_(c)). Accordingly, it can be said that a material has more superior magnetic properties as the material is more soft magnetic.

In the case x=0, that is, FeAl₂O₄ (hercynite) powder, as illustrated in FIG. 12A, a value of B increases with increase in a value of H, and the B—H characteristics are represented by a line. FeAl₂O₄ is a paramagnetic substance, and thus it can be said that the result that the B—H characteristics are represented by the line is reasonable.

Moreover, regarding Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0.2, as illustrated in FIG. 12B, the B—H characteristics are represented by a hysteresis curve. Accordingly, it has been found that Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0.2 is a ferromagnetic substance. It is to be noted that regarding a range 0<x<0.2 of the value of x, although it is not possible to determine from FIG. 12A and FIG. 12B that Fe(Al_(1−x)Mn_(x))₂O₄ is a ferromagnetic substance, it can be said from FIG. 12B that Fe(Al_(1−x)Mn_(x))₂O₄ is a ferromagnetic substance at least in the case x=0.2.

Moreover, regarding Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0.6, 0.7, 0.8, 0.9, as illustrated in FIG. 12C to FIG. 12F, the B—H characteristics are represented by a hysteresis curve. Accordingly, it has been found that Fe(Al_(1−x)Mn_(x))₂O₄ in the case x=0.6, 0.7, 0.8, 0.9 is a ferromagnetic substance.

Moreover, it has been found that a difference between positive and negative values of the external magnetic field H when the magnetic flux density is 0 in the hysteresis curve decreases (the coercivity H_(c) decreases) with increase in the value of x as in x=0.2, 0.6, 0.7, 0.8, 0.9, and the hysteresis curve indicates the soft magnetism. As a result, it has been found that Fe(Al_(1−x)Mn_(x))₂O₄ having more superior magnetic properties is obtained as the value of x is greater for Fe(Al_(1−x)Mn_(x))₂O₄.

It can be said from the above that Fe(Al_(1−x)Mn_(x))₂O₄ is a ferromagnetic substance in the case x≧0.2.

FIG. 13 is a graph illustrating a relationship between a value of x in Fe(Al_(1−x)Mn_(x))₂O₄ and a mass magnetic susceptibility σ_(s).

As illustrated in FIG. 13, a value of mass magnetic susceptibility σ_(s) increases with increase in the value of x in Fe(Al_(1−x)Mn_(x))₂O₄. Consequently, it can be said that Fe(Al_(1−x)Mn_(x))₂O₄ having more superior magnetization per unit mass is obtained as the value of x is greater. Moreover, when Fe(Al¹⁻Mn_(x))₂O₄ is used in a field in which high magnetic properties are needed, especially such as high-frequency devices, it is desirable that Fe(Al_(1−x)Mn_(x))₂O₄ be a material having superior saturation magnetic flux density. There is a close relationship between saturation magnetic flux density and mass magnetic susceptibility, and it is desirable that mass magnetic susceptibility σ_(s) be expressed as, for example, σ_(s)≧10. Accordingly, it is desirable that Fe(Al_(1−x)Mn_(x))₂O₄ whose mass magnetic susceptibility σ_(s) satisfies σ_(s)≧10 be synthesized.

FIG. 14 is a graph illustrating a relationship between a value of x in Fe(Al_(1−x)Mn_(x))₂O₄ and a saturation magnetic flux density B_(s).

As illustrated in FIG. 14, a value of the saturation magnetic flux density B_(s) increases with increase in the value of x in Fe(Al_(1−x)Mn_(x))₂O₄. Consequently, it can be said that Fe(Al_(1−x)Mn_(x))₂O₄ having more superior saturation magnetic flux density B_(s) as the value of x is greater.

FIG. 15 is a graph illustrating a relationship between a value of x in Fe(Al_(1−x)Mn_(x))₂O₄ and a coercivity H. It is to be noted that the coercivity (vertical axis) is represented by a logarithm in FIG. 15.

As illustrated in FIG. 15, the coercivity H_(c) decreases with increase in the value of x in Fe(Al_(1−x)Mn_(x))₂O₄. It can be said that this indicates that Fe(Al_(1−x)Mn_(x))₂O₄ is further soft magnetized with increase in the value of x. The coercivity H_(c) indicates the minimum value when the value of x is approximately 0.8. The coercivity increases again when the value of x exceeds 0.8. Accordingly, it can be said that when the value of x is approximately 0.8, Fe(Al_(1−x)Mn_(x))₂O₄ exhibiting the best soft magnetism and having the best coercivity is obtained.

FIG. 16 is a table summarizing a relationship between values of x in Fe(Al_(1−x)Mn_(x))₂O₄ and structures and magnetic properties of Fe(Al_(1−x)Mn_(x))₂O₄.

As illustrated in FIG. 16, in the case x=0.2, a Fe(Al_(1−x)Mn_(x))₂O₄ solid solution was successfully synthesized by the above-described production method for the first time.

Moreover, although a single phase was not obtained by heat treatment at a normal temperature in the case x=0.4 or 0.5, single-phase powder was successfully synthesized by, for example, pulsed electric-current pressure sintering in the case x=0.5. Furthermore, also in the case x=0.6, 0.7, 0.8, 0.9, a Fe(Al¹⁻Mn_(x))₂O₄ solid solution was successfully synthesized by the above-described production method for the first time.

As stated, Fe(Al_(1−x)Mn_(x))₂O₄ produced by the above-described production method is ferrite having a new composition and exhibits ferromagnetism. Fe(Al_(1−x)Mn_(x))₂O₄ has saturation magnetic flux density B_(s) in a range of from approximately 0.06 to 0.11 [T] as an example, and coercivity H_(c) in a range of from 14 to 18 [Oe] as an example. Moreover, it has been evaluated that the value of x in Fe(Al_(1−x)Mn_(x))₂O₄ when Fe(Al_(1−x)Mn_(x))₂O₄ has the best magnetic properties is, for example, 0.8, and at this time the saturation magnetic flux density B_(s) and coercivity H_(c) are 0.098 [T] and 14 [Oe], respectively.

According to the magnetic material and production method therefor according to the embodiment, because it is possible to place Mn in the same site as the site in which Al of hercynite FeAl₂ 0 ₄ is placed, it is possible to easily synthesize a ferrite magnetic material expressed by a chemical structure formula Fe(Al_(1−x)Mn_(x))₂O₄. In consequence, it is possible to provide a ferrite magnetic material Fe(Al_(1−x)Mn_(x))₂O₄ having high magnetic properties.

Although the magnetic material and production method therefor according to the embodiment of the present disclosure have been described above, the present disclosure is not limited to the embodiment.

For example, a sintering method is not limited to the aforementioned hot pressing, and other methods such as pulsed electric-current pressure sintering may be used. Moreover, the temperatures and times in the aforementioned steps are mere examples, and other temperatures and times may be used.

Moreover, the solution 1 a, the solution 1 b, and the solution 1 c may be mixed at one time, or, for example, a mixed solution obtained by mixing the solution 1 b and the solution 1 c may be prepared, and the mixed solution may be further mixed with the solution 1 a.

Moreover, although Fe(Al_(1−x)Mn_(x))₂O₄ is synthesized by a liquid phase method in which the solution 1 a, the solution 1 b, and the solution 1 c are mixed in the aforementioned embodiment, Fe(Al_(1−x)Mn_(x))₂O₄ may be synthesized by the solid phase method.

Moreover, the present disclosure is not limited to the embodiment. Forms obtained by various modifications to the embodiment that can be conceived by a person skilled in the art as well as forms realized by combining structural elements in different embodiments, which are within the scope of the essence of the present disclosure, may be included in the one or more aspects.

INDUSTRIAL APPLICABILITY

A magnetic material according to the present disclosure can be used for inductors for high frequency, magnetic cores for transformers, and the like.

REFERENCE SIGNS LIST

-   1 a solution (mixed aqueous solution) -   1 b solution (citric acid) -   1 c solution (ethylene glycol) 

1. A magnetic material which is expressed by a chemical structure formula Fe(Al_(1−x)Mn_(x))₂O₄, where 0<x<1, and exhibits ferromagnetism.
 2. The magnetic material according to claim 1, wherein a range of a value of mass magnetic susceptibility σ_(s) [emu/g] of the magnetic material is expressed as σ_(s)≧10.
 3. The magnetic material according to claim 1, wherein a range of a value of x is expressed as x≧0.2.
 4. The magnetic material according to claim 1, wherein the magnetic material comprises manganese dioxide MnO₂ as a raw material.
 5. A production method for a magnetic material, wherein the magnetic material is expressed by a chemical structure formula Fe(Al_(1−x)Mn_(x))₂O₄, where 0<x<1, and exhibits ferromagnetism, the production method comprising: preparing a mixed aqueous solution by dissolving, in distilled water, Fe nitrate, Al nitrate, and an oxide including Mn, the Fe nitrate, the Al nitrate, and the oxide being parent materials; preparing a metal-citric acid complex by mixing citric acid and ethylene glycol with the mixed aqueous solution; obtaining a precursor by boiling the metal-citric acid complex to a gel and drying the gel; and obtaining the magnetic material by sintering the precursor.
 6. The production method according to claim 5, wherein, in the obtaining of the magnetic material, a trivalent Fe ion and a tetravalent Mn ion are reduced to a divalent Fe ion and a trivalent Mn ion, respectively.
 7. The production method according to claim 5, wherein the Fe nitrate is iron(III) nitrate nonahydrate Fe(NO₃)₃.9H₂O, the Al nitrate is aluminum(III) nitrate nonahydrate Al(NO₃)₂.9H₂O, and the oxide including Mn is manganese dioxide MnO₂.
 8. The production method according to claim 5, wherein, in the preparing of the metal-citric acid complex, a molar ratio among a metal ion, the citric acid, and the ethylene glycol in the mixed aqueous solution is 1:3:9.
 9. The magnetic material according to claim 2, wherein a range of a value of x is expressed as x≧0.2.
 10. The magnetic material according to claim 2, wherein the magnetic material comprises manganese dioxide MnO₂ as a raw material.
 11. The magnetic material according to claim 3, wherein the magnetic material comprises manganese dioxide MnO₂ as a raw material.
 12. The magnetic material according to claim 9, wherein the magnetic material comprises manganese dioxide MnO₂ as a raw material.
 13. The production method according to claim 6, wherein the Fe nitrate is iron(III) nitrate nonahydrate Fe(NO₃)₃.9H₂O, the Al nitrate is aluminum(III) nitrate nonahydrate Al(NO₃)₂.9H₂O, and the oxide including Mn is manganese dioxide MnO₂.
 14. The production method according to claim 6, wherein, in the preparing of the metal-citric acid complex, a molar ratio among a metal ion, the citric acid, and the ethylene glycol in the mixed aqueous solution is 1:3:9.
 15. The production method according to claim 7, wherein, in the preparing of the metal-citric acid complex, a molar ratio among a metal ion, the citric acid, and the ethylene glycol in the mixed aqueous solution is 1:3:9.
 16. The production method according to claim 13, wherein, in the preparing of the metal-citric acid complex, a molar ratio among a metal ion, the citric acid, and the ethylene glycol in the mixed aqueous solution is 1:3:9. 